Fluorous and organic extraction systems; A Comparison from the perspectives of coordination structures, interfaces, and bulk extraction phases

Ueda, Yuki; Micheau, C.; Akutsu, Kazuhiro*; Tokunaga, Kohei; Yamada, Masako*; Yamada, Norifumi*; Bourgeois, D.*; Motokawa, Ryuhei

Langmuir, 40(46), p.24257 - 24271, 2024/11

https://doi.org/10.1021/acs.langmuir.4c02268

Microscopic structures in liquid-liquid extraction, such as structuration between extractants or extracted complexes in bulk organic phases and at interfaces, can influence macroscopic phenomena, such as the distribution behavior of solutes, including extraction efficiency, selectivity, and phase separation of the organic phase. In this study, we correlated the macroscopic behavior of the extraction of Zr(IV) ions from nitric acid solutions with microscopic structural information in order to understand at the molecular level the key factors contributing to the higher metal ion extraction performance in the fluorous extraction system comprising fluorous phosphate (TFP) in perfluorohexane as compared to the analogous organic extraction system comprising organic phosphate (THP) in n-hexane. Extended X-ray absorption fine structure, neutron reflectometry, and small-angle neutron scattering revealed the local coordination structure around the Zr(IV) ion, the accumulation of extractant molecules at the interface, and the structuration of extractant molecules in the bulk extraction phase, respectively. In the fluorous extraction system, extractant aggregates with were formed after contact with nitric acid. In contrast, in the organic extraction system, only extractant dimers were formed. We speculate that differences in the local coordination structure around the Zr(IV) ion and the structuration of the extractant molecules in the bulk extraction phase contribute to the high Zr(IV) extraction performance in the fluorous extraction system. In particular, the size of the aggregates hardly changed with increasing Zr(IV) concentration in the fluorous phase, which may be closely related to the absence of phase splitting in the fluorous extraction system.

Degradation of a lithium cobalt oxide cathode under high voltage operation at an interface with an oxide solid electrolyte

Ito, Kotaro*; Tamura, Kazuhisa; Shimizu, Keisuke*; Yamada, Norifumi*; Watanabe, Kenta*; Suzuki, Kota*; Kanno, Ryoji*; Hirayama, Masaaki*

RSC Applied Interfaces (Internet), 1(4), p.790 - 799, 2024/04

https://doi.org/10.1039/D3LF00251A

LiCoO is widely used as a cathode material in lithium-ion batteries. However, the reversible capacity of LiCoO at high voltage is not well known because of the oxidative degradation of the electrolyte. In this study, a thin-film all-solid-state battery was fabricated with epitaxially grown LiCoO cathode and LiPO solid electrolyte as a model battery that operates stably at high voltages, ranging up to 4.6 V, without drastic degradation. However, the charge-discharge capacities of the battery decreased with cycling at 4.7 V. synchrotron X-ray diffraction studies revealed that LiCoO was deactivated via a change in its crystal structure to O1 type, with narrow interlayer distances, at 4.7 V. The reduced distance between the interlayers in the O1 structure possibly prevents the re-intercalation of Li ions, leading to irreversibility.

Interfacial distribution of Nafion ionomer thin films on nitrogen-modified carbon surfaces

Yoshimune, Wataru*; Kikkawa, Nobuaki*; Yoneyama, Hiroaki*; Takahashi, Naoko*; Minami, Saori*; Akimoto, Yusuke*; Mitsuoka, Takuya*; Kawaura, Hiroyuki*; Harada, Masashi*; Yamada, Norifumi*; et al.

ACS Applied Materials & Interfaces, 14(48), p.53744 - 53754, 2022/11

https://doi.org/10.1021/acsami.2c14574

New design of a sample cell for neutron reflectometry in liquid-liquid systems and its application for studying structures at air-liquid and liquid-liquid interfaces

Akutsu-Suyama, Kazuhiro*; Yamada, Norifumi*; Ueda, Yuki; Motokawa, Ryuhei; Narita, Hirokazu*

Applied Sciences (Internet), 12(3), p.1215_1 - 1215_10, 2022/02

https://doi.org/10.3390/app12031215

no abstracts in English

Multilayered lamellar materials and thin films by instant self-assembly of amphiphilic random copolymers

Ikami, Takaya*; Watanabe, Yuki*; Ogawa, Hiroki*; Takenaka, Mikihito*; Yamada, Norifumi*; Ouchi, Makoto*; Aoki, Hiroyuki; Terashima, Takaya*

ACS Macro Letters (Internet), 10(12), p.1524 - 1528, 2021/12

https://doi.org/10.1021/acsmacrolett.1c00571

Water distribution in Nafion thin films on hydrophilic and hydrophobic carbon substrates

Ito, Kanae; Harada, Masashi*; Yamada, Norifumi*; Kudo, Kenji*; Aoki, Hiroyuki; Kanaya, Toshiji*

Langmuir, 36(43), p.12830 - 12837, 2020/11

https://doi.org/10.1021/acs.langmuir.0c01917

Materials and Life Science Experimental Facility (MLF) at the Japan Proton Accelerator Research Complex, 2; Neutron scattering instruments

Nakajima, Kenji; Kawakita, Yukinobu; Ito, Shinichi*; Abe, Jun*; Aizawa, Kazuya; Aoki, Hiroyuki; Endo, Hitoshi*; Fujita, Masaki*; Funakoshi, Kenichi*; Gong, W.*; et al.

Quantum Beam Science (Internet), 1(3), p.9_1 - 9_59, 2017/12

https://doi.org/10.3390/qubs1030009

The neutron instruments suite, installed at the spallation neutron source of the Materials and Life Science Experimental Facility (MLF) at the Japan Proton Accelerator Research Complex (J-PARC), is reviewed. MLF has 23 neutron beam ports and 21 instruments are in operation for user programs or are under commissioning. A unique and challenging instrumental suite in MLF has been realized via combination of a high-performance neutron source, optimized for neutron scattering, and unique instruments using cutting-edge technologies. All instruments are/will serve in world-leading investigations in a broad range of fields, from fundamental physics to industrial applications. In this review, overviews, characteristic features, and typical applications of the individual instruments are mentioned.

Seismic interferometry using long time measured microtremor

Yamada, Nobuto*; Ishigaki, Koichi*; Yamaguchi, Shinji*; Narita, Norifumi*; Matsuoka, Toshiyuki; Hodotsuka, Yasuyuki; Matsuoka, Toshifumi*

Shadan Hojin Butsuri Tansa Gakkai Dai-117-Kai (Heisei-19-Nendo Shuki) Gakujutsu Koenkai Koen Rombunshu, p.146 - 148, 2007/10

Seismic interferometry synthesizes the Green's function between two receivers by calculating cross-correlation of records measured at their locations. In Japan Atomic Energy Agency(JAEA), Seismic Interferometry using blasting vibration caused by the shafts excavation had been carried out to investigate the geologic structure in the surrounding area. The result was identical to the existing seismic reflection section. In this study, we applied this technique to long time measured microtremor. The result was also identical to the results of existing section and seismic interferometry using blasting vibration caused by the shafts excavation.

Potential of aggregation control for solvent extraction separation

Micheau, C.; Motokawa, Ryuhei; Ueda, Yuki; Akutsu-Suyama, Kazuhiro*; Yamada, Norifumi*; Yamada, Masako*; Bourgeois, D.*; Berthon, L.*

no journal, , 

Differences in extraction mechanisms between fluorous and organic extraction systems; Structuring extractants at the interface and in the bulk extracting phase

Ueda, Yuki; Micheau, C.; Tokunaga, Kohei; Akutsu, Kazuhiro*; Yamada, Norifumi*; Motokawa, Ryuhei

no journal, , 

no abstracts in English